Cyanine dye



Patented June 6, 1939 PATENT OFFICE ICYANINE DYE Walter Dieterle, 'Dessau-Ziebigk in Anhalt, and

Robert Walter, Wolfen, Kreis Bitterfeld, Germany, and Hermann Diirr, Binghamton, N. Y., assignors, by mesne assignments, to Agfa Ansco Corporation, Binghamton, N. Y., a corporation of Delaware No Drawing. Application December 2, 1933, Se-

rial No. 700,750. In Germany January 13,

11 Claims.

Our present invention relates to selenopseudocyanines. It is a continuation-in-part of our co-pending application Ser. No. 586,056 filed Jan. 11, 1932. 7 One of its objects is a process of manufacturing selenopseudocyanines. Another object are the selenopseudocyanines. Further objects will be seen from the detailed specification following hereafter.

We have found that selenopseudocyanines of the general formula:

i V and W=I-I, alkyl, alkoxy, substituted amino groups, benzene, halide,

r and r'=alkyl,

A=H, alkyl,

X=halide, perchlorate, para-toluene sulfonate, alkylosulfate, nitrate,or another suitable anion,

can be easily prepared by acting onthe quaternary salt of a suitable selenazole base with'the quaternary salt of a -2-iodoquinoline in the presence of alkali.

The selenopseudocyanines are particularly 3O 1 suitable for the sensitizing of emulsion layers for producing part-color pictures, since, as" compared with the known sensitizers, they have a better selection capacity for the samespectral region.

In the general formula Vand W may take any position in the benzene nuclei, however, the5 and 6 position and the 6' and 7' position are preferred. V and W may represent alkyl, for instance, methyl, ethyl, etc., or an alkoxy group, for instance, a methoxy or ethoxy group, or an amino group both hydrogen atoms .of which are replaced by alkyl or one of the hydrogen atoms being replaced by alkyl and the other by aryl and finally one of thehydrogen atoms being rethan that containing the anion to be replaced, the dye can be obtained by interaction of the latter dye withan easily soluble salt of the anion to be introduced, for instance, the sodium salt of the said anion. If the anion to be introduced into the molecule yields a dye of increased solubility, there is used a salt of the anion With a cation which forms an insoluble salt with the anion to be replaced. For this purpose the silver salt of the anion to be introduced will in most cases be suitable, since in the manufacture of the selenopseudocyanine dyes from the ethiodides of the parent bases, the dye will usually be precipitated in the form of a halide, generally the iodide.

The following examples serve to illustrate our invention.

Example 1.-For producing the dye 1.1'-diethyl-2.2'- (benzselenoquino) -cyanine-iodide corresponding to the formula Se 5 a on: 6 2 2' 7 si -s 1 CH3 \I 02 5 7 grams of 2-ethyl-benzselenazole-methyl-iodide and 8 grams of 2-iod0-quinoline-ethyl-iodide in 100 grams of boiling alcohol are mixed with cc. of an alcoholic solution of caustic potassium of 4 per cent strength. After cooling the dye precipitates in form of orange colored needles.

The alcoholic solution of the dye shows an absorption maximum at a wave length of about 490 .[L/L.

Example 3.-For producing the dye 1.l'-diethyl-2.2 (benzseleno -6' -methylquino) -cyanineiodide corresponding to the formula to the boiling solution of 7 grams of Z-methylbenzselenazole-ethyl-iodide and 8.5 grams of Y2- iodo-p-toluquino-ethyl-iodide in cc. of alcohol, there are gradually added 20 cc. of an alcoholic solution of caustic potassium of 4 per cent strength. The dye is precipitated by cooling. It crystallizes from alcohol in form of orange colcred little rods.

The alcoholic solution of the dye shows an absorption maximum at a wave length of about 495 aa.

Example 4.-For producing the dye 1.ll-diethyl 2.2 (benzseleno 5'5 benzo quino) cyanine-iodide corresponding to the formula 02115 I 0235 a mixture of 7 grams of 2-methyl-benzselenazoleethyl-iodide and 9 grams of Z-iodo-e-naphthoquino-ethyl-iodide are boiled with 100 cc. of alcohol and then 20 cc. of an alcoholic solution of' caustic potassium of 4 per cent strength are gradually added, whereby the dye separates in form of dark orange red crystals.

The alcoholic solution of the dye shows an absorption maximum at a wave length of about 510 a l.

Example 5.-Fo-r producing the dye 1.1'-diethyl-2.2-(fi-methoxy-benzseleno 6 methoxyquino) -cyanine-iodide corresponding to the formula ethyl-2.2'-( G-methyl benzseleno 8' methoxyquino)-cyanine-iodide corresponding to the formula 6 I I 6 H 3 6 E30 6 1 1' 7 N N s Y 02115 I CH3 4 grams of 2.5-dimethyl-benzselenazole-ethyliodide and 4.5 grams of 8-methoxy-2-iodo-quinoline-ethyliodide are dissolved in hot alcohol. The solution is boiled and is while boiling mixed with 10 cc. of an alcoholic solution of caustic potassium of 4 per cent strength. While cooling the dye precipitates in form of orange red crystals.

The alcoholic solution of the dye shows an absorption maximum at a wave length of about 500 l.

Example 7.For producing the dye l-methyl- 1'-ethyl-2.2 (5 iodo benzseleno 6' methylquino)-cyanine-iodide corresponding to the for- 4.5 grams of 6-iodine-2-methyl-benzselenazoleethyl-iodide and 4 grams of 2-iodo-p-to1u-=quinoline-ethyl-iodide are dissolved in 100 cc. of hot alcohol. The boiling solution is mixed with 10 cc. of an alcoholic solution of caustic potassium of 4 per cent strength and heating is continued for 10 minutes. After cooling the dye separates in form of orange red crystals.

The alcoholic solution of the dye shows an absorption maximum at a wave length of about 495 r.

Example 8.-For the production of the dye 1.1- diethy1-2.2'-(6.6 diethoxy benzseleno quino) cyanine-iodide corresponding to the formula 4.5 grams of 5-ethoxy-Z-methyl-benzselenazoleethyl-iodide and 4 grams of G-ethoxy-Z-iodoquino-ethyl-iodide are heated with 100 cc. of alcohol until boiling and then mixed with 10 cc. of an alcoholic solution of caustic potassium of 4 per cent strength and kept boiling for about 10 minutes. little rods.

The alcoholic solution of the dye shows an absorption maximum at a Wave length of about 510 [Lil/- Example 9.-For producing the dye l-methyl- 1-ethyl-2.2'-(4.5-benzo-benzseleno- 6 methylquino) -cyanine-chloride corresponding to the formula 4 4' 5" is g H m 6 1 2| 5; 7

The dye separates in form of reddish ethyl-iodide and 4 grams of 2-iodo-7-methylconcentrated aqueous solution of ammonia by The alcoholic solution of the dye shows an absorption'maximum at a wave length of about C2115 I v 3.5 grams of 5-chloro-2-methyl-benzselenazolequino-ethyl-iodide are boiled with 100 cc. of alcohol and to the boiling mixture there are added cc. of an alcoholic solution of caustic potassium of. 4 per cent strength. While cooling the reaction mixture the dye separates. It crystallizes from its alcoholic solution in form of small felted crystals.

'Ihealcoholic solution of the dye shows an absorption maximum at a wave length of about may be made by boiling 2 grams of 6-amino-2- 7 V pionyl-amino-2-methyl-benzselenazole definite absorption maximum at a wave length of about 520 ,up.

Example 12.-The dye 1-methyl-1'-ethyl-5 propionylamino 6 methyl-selenopseudocyanine iodide corresponding with the formula may be obtained by dissolving 2 grams of G-promethiodide and 2 grams of 2-iodo-6-methylquinoline ethiodide in cc. of boiling alcohol and adding to the boiling solution 4 cc. of an alcoholic solution of sodium ethylate of 3 per cent. strength. The mixture assumes a red color. arates in the form of orange flakes after cooling. Recrystallization from alcohol yields orange-red felted needles.

The alcoholic solution of the dye has an absorption maximum at a wave length of about Example 13.-The dye 1-methyl-1'-ethyl-5- The dye sep-.

butyrylamino-fi'-methyl-selenopseudocyanine iodide corresponding with the formula C nHs may be obtained from 6-butyrylamino-2-methylbenzselenazole methiodide and 2-iodo-6-methylquinoline ethiodide in a manner analogous to that described in Example 2.

The alcoholic solution. of the dye has an absorption maximum atua .wave length of about 505 ,ua.

It is to be understood that our invention is not limited to the foregoing examples nor to the specific details given therein. Numerous other embodiments are possible and we contemplate as included within our invention. all such modifications and equivalents as fall within the scope of the appended claims. So, for instance, the benzene nuclei may contain one or more substituents. The nomenclature used is arbitrary, but it is familiar to every chemist skilled in the art and has the advantage of clearness. Numbering of the bases is commenced from the selenium atom of the heterocyclic ring and numbering of the dyes is commenced from the nitrogen atom of the heterocyclic ring. The formulae of the dyes as given herein represent the molecular structure of our new dyes so far as known.

What we claim is:

1. The process of producing a selenopseudocyam'ne which comprises acting .on a quaternary salt of a 2-ethylbenzselenazole with a quaternary salt of a Z-iodoquinoline in the presence of alkali.

2. The process of producing a selenopseudocyanine which comprises boiling Z-ethylbenzselenazole ethiodide with a quaternary salt of a 2- iodoquinoline in alcoholic solution in the presence of caustic potassium.

3. A 1.1'-dialkylbenzseleno-pseudocyanine salt.

- 4. A selenopseudocyanine corresponding with the formula -Se R R f I r X r R being a member of the group consisting of naphthylene and R being a member of the group consisting of naphthylene and V and W being members of the group consisting of H, alkyl, alkoxy, amino groups, an amino group substituted by the radical of a lower fatty acid and halogen,

r and r being alkyl,

A being a radical selected from the group consisting of H and alkyl, and

X being an anion capable of precipitating the dye.

r 5. Aselenopseudocyanine corresponding with the formula B being a member of the group consisting of naphthylene and R, being a member of the group consisting of naphthylene and V and W being members of the group consisting of H, alkyl, alkoxy, amino groups, an amino group substituted by the radical of a lower fatty acid and halogen, r and 1' being alkyl, X being an anion capable of precipitating the dye.

6. The dye 1.1 diethyl 2.2 (benzseleno quino) -cyanine-iodide corresponding with the formula having in its alcoholic solution an absorption maximum at a wave length of about 490 7. The dye 1.1-diethyl-2.2'-(benzseleno-5'.6- benz-quino)-cyanine-iodide corresponding with the formula 9. The process of producing a selenopseudocyanine which comprises acting on a quaternary salt of a 2-ethyl benzselenazole with a quaternary salt of a 2-iodo-quinoline in the presence of a strong base. v 30 10. An [N-alkyl-benzselenazole (2)1-[N-a1kylquinoline (2)1-methinecyanine salt. a

11. An [N-alkyl-benzselenazole (2)1-[N-alkylquinoline (2) ]-meso-methyl-methinecyanine salt WALTER DIETERLE. ROBERT WAIETER. HERMANN DURR. 

